Rapid dye degradation with reactive oxidants generated by chloride-induced peroxymonosulfate activation

Transition-metal is known to catalyze peroxymonosulfate (PMS) decomposition to produce sulfate radicals. Here we report reactions between PMS and chloride, without a need of transition metals, also can be used to degrade organic dye pollutant (Rhodamine B, (RhB)). Some important operating parameters, such as dosages of PMS and Cl^?, pH of solution, temperature, ionic strength, and several common cations, were systematically investigated. Almost complete decoloration of RhB was achieved within 5 min ([PMS]?=?0.5 mM, [Cl^?]?=?120 mM, and pH 3.0), and RhB bleaching rate increased with the increased dosages of both PMS and chloride ion, following the pseudo-first-order kinetic model. However, the total organic carbon (TOC) removal results demonstrated that the decoloration of RhB was due to the destruction of chromophore rather than complete degradation. RhB decoloration could be significantly accelerated due to the high ionic strength. Increasing of the reaction temperature from 273 K to 333 K was beneficial to the RhB degradation, and the activation energy was determined to be 32.996 kJ/mol. Bleaching rate of RhB with the examined cations increased with the order of NH₄ ⁺?<?Na⁺?<?K⁺?<?Al³⁺?<?Ca²⁺?<?Mg²⁺. Some major degradation products of RhB were identified by GC-MS. The present study may have active technical implications for the treatment of dyestuff wastewater in practice.     

Degradation of polycyclic aromatic hydrocarbons in a coking wastewater treatment plant residual by an O3/ultraviolet fluidized bed reactor

Coking wastewater treatment plant (CWWTP) represents a typical point source of polycyclic aromatic hydrocarbons (PAHs) to the water environment and threatens the safety of drinking water in downstream regions. To enhance the removal of residual PAHs from bio-treated coking wastewater, a pilot-scale O₃/ultraviolet (UV) fluidized bed reactor (O₃/UV FBR) was designed and different operating factors including UV irradiation intensity, pH, initial concentration, contact time, and hydraulic retention time (HRT) were investigated at an ozone level of 240 g h^?1 and 25?±?3 °C. A health risk evaluation and cost analysis were also carried out under the continuous-flow mode. As far as we know, this is the first time an O₃/UV FBR has been explored for PAHs treatment. The results indicated that between 41 and 75 % of 18 target PAHs were removed in O₃/UV FBR due to synergistic effects of UV irradiation. Both increased reaction time and increased pH were beneficial for the removal of PAHs. The degradation of the target PAHs within 8 h can be well fitted by the pseudo-first-order kinetics (R ²?>?0.920). The reaction rate was also positively correlated with the initial concentrations of PAHs. The health risk assessment showed that the total amount of carcinogenic substance exposure to surface water was reduced by 0.432 g day^?1. The economic analysis showed that the O₃/UV FBR was able to remove 18 target PAHs at a cost of US$0.34 m^?3. These results suggest that O₃/UV FBR is efficient in removing residuals from CWWTP, thus reducing the accumulation of persistent pollutant released to surface water.     

Cytotoxicity,genotoxicity and oxidative stress of malachite green on the kidney and gill cell lines of freshwater air breathing fish Channa striata

The cytotoxicity, genotoxicity and oxidative stress of malachite green (MG) was investigated using the fish Channa striata kidney (CSK) and Channa striata gill (CSG) cell lines. Five concentrations ranging from 0.001 to 10 μg mL^?1 were tested in three independent experiments. Cytotoxicity was assessed by 3-(4, 5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay, Rhodamine 123 and Alamar Blue. The mitochondrial changes and apoptosis of MG-exposed cells were observed by Rhodamine 123 and acridine orange/ethidium bromide (AO/EB) staining, respectively. In vitro potential DNA damaging effect of MG was tested using comet assay. Mitochondrial damage, apoptosis and DNA fragmentation increased in a concentration-dependent manner. Additionally, DNA electrophoretic mobility experiments were carried out to study the binding effect of MG to double-stranded DNA (dsDNA) of cells. DNA shift mobility experiments showed that MG is capable of strongly binding to linear dsDNA causing its degradation. Biochemical parameters such as lipid peroxidation (MDA), catalase (CAT) activity and reduced glutathione (GSH) levels were evaluated after exposure to MG. In CSK and CSG cell lines exposed to MG for 48 h, a significant increase in lipid peroxidation, which might be associated with decreased levels of reduced glutathione and catalase activity in these cell lines (p?相似文献   

Heterogeneous Fenton-like discoloration of Rhodamine B using natural schorl as catalyst: optimization by response surface methodology

A cationic dye, Rhodamine B (RhB), could be efficiently discolored by heterogeneous Fenton-like reaction catalyzed by natural schorl. In this work, with the main goal of the optimization for RhB discoloration, central composite design under the response surface methodology (RSM) was employed for the experiment design and process optimization. The significance of a second-order polynomial model for predicting the optimal values of RhB discoloration was evaluated by the analysis of variance and 3D response surface and counter plots for the interactions between two variables were constructed. The Pareto graphic analysis of the discoloration process indicated that, among all the variables, solution pH (X ₃, 47.95 %) and H₂O₂ concentration (X ₁, 24.39 %) had the largest influences on the heterogeneous Fenton-like discoloration of RhB. Based on the model prediction, the optimum conditions for RhB discoloration were determined to be 45 mM H₂O₂ concentration, 2.5 g/L schorl dosage, solution pH 2, and 110 min reaction time, with the maximum RhB discoloration ratio of 98.86 %. The corresponding experimental value of RhB discoloration ratio under the optimum conditions was determined as 99.31 %, which is very close to the optimized one, implying that RSM is a powerful and satisfactory strategy for the process optimization.     

Enhancement of in vitro high-density polyethylene (HDPE) degradation by physical,chemical, and biological treatments

Partially degraded high-density polyethylene (HDPE) was collected from plastic waste dump yard for biodegradation using fungi. Of various fungi screened, strain MF12 was found efficient in degrading HDPE by weight loss and Fourier transform infrared (FT-IR) spectrophotometric analysis. Strain MF12 was selected as efficient HDPE degraders for further studies, and their growth medium composition was optimized. Among those different media used, basal minimal medium (BMM) was suitable for the HDPE degradation by strain MF12. Strain MF12 was subjected to 28S rRNA sequence analysis and identified as Aspergillus terreus MF12. HDPE degradation was carried out using combinatorial physical and chemical treatments in conjunction to biological treatment. The high level of HDPE degradation was observed in ultraviolet (UV) and KMnO₄/HCl with A. terreus MF12 treatment, i.e., FT10. The abiotic physical and chemical factors enhance the biodegradation of HDPE using A. terreus MF12.     

Study on biodegradation process of lignin by FTIR and DSC

The biodegradation process of lignin by Penicillium simplicissimum was studied to reveal the lignin biodegradation mechanisms. The biodegradation products of lignin were detected using Fourier transform infrared spectroscopy (FTIR), UV–Vis spectrophotometer, different scanning calorimeter (DSC), and stereoscopic microscope. The analysis of FTIR spectrum showed the cleavage of various ether linkages (1,365 and 1,110 cm^?1), oxidation, and demethylation (2,847 cm^?1) by comparing the different peak values in the corresponding curve of each sample. Moreover, the differences (T_m and ΔH_m values) between the DSC curves indirectly verified the FTIR analysis of biodegradation process. In addition, the effects of adding hydrogen peroxide (H₂O₂) to lignin biodegradation process were analyzed, which indicated that H₂O₂ could accelerate the secretion of the MnP and LiP and improve the enzymes activity. What is more, lignin peroxidase and manganese peroxidase catalyzed the lignin degradation effectively only when H₂O₂ was presented.     

Biodegradability of a polyacrylate superabsorbent in agricultural soil

Superabsorbent polymers (SAP) are used, inter alia, as soil amendment to increase the water holding capacity of soils. Biodegradability of soil conditioners has become a desired key characteristic to protect soil and groundwater resources. The present study characterized the biodegradability of one acrylate based SAP in four agricultural soils and at three temperatures. Mineralisation was measured as the ¹³CO₂ efflux from ¹³C-labelled SAP in soil incubations. The SAP was either single-labelled in the carboxyl C-atom or triple-labelled including additionally the two C-atoms interlinked in the SAP backbone. The dual labelling allowed estimating the degradation of the polyacrylate main chain. The ¹³CO₂ efflux from samples was measured using an automated system including wavelength-scanned cavity ring-down spectroscopy. Based on single-labelled SAP, the mean degradation after 24 weeks varied between 0.45 % in loamy sand and 0.82 % in loam. However, the differences between degradation rates in different soils were not significant due to a large intra-replicate variability. Similarly, mean degradation did not differ significantly between effective temperature regimes of 20° and 30 °C after 12 weeks. Results from the triple-labelled SAP were lower as compared to their single-labelled variant. Detailed results suggest that the polyacrylate main chain degraded in the soils, if at all, at rates of 0.12–0.24 % per 6 months.     

Photocatalytic degradation of molinate in aqueous solutions

In this study, the degradation of molinate through heterogeneous photocatalysis, using two different types of the semiconductor TiO₂ as photocatalyst, as well as through homogeneous treatment, applying the photo-Fenton reaction, has been investigated. As far as heterogeneous photocatalysis is concerned, the degradation of the pesticide follows apparent first-order kinetics, while the type of the catalyst and the pH value of the solution affect the degradation rate. The effect of the addition of electron scavengers (H₂O₂ and K₂S₂O₈) was also studied. In the case of photo-Fenton-assisted system, the degradation also follows pseudo-first-order kinetics. Parameters such as iron’s and electron scavenger’s concentration and inorganic ions strongly affect the degradation rate. The extent of pesticide mineralization was investigated using dissolved organic carbon (DOC) measurements. The toxicity of the treated solution was evaluated using the Microtox test based on the luminescent bacteria Vibrio fischeri. The detoxification and mineralization efficiency was found to be dependent on the system studied, and although it did not follow the rate of pesticide disappearance, it took place in considerable extent. The study of the photodegradation treatment was completed by the determination of the intermediate by-products formed during the process, which was carried out using LC-MS/MS technique and led to similar compounds with both processes.     

Oxidative stress response in dye degrading bacterium Lysinibacillus sp. RGS exposed to Reactive Orange 16, degradation of RO16 and evaluation of toxicity

Lysinibacillus sp. RGS degrades sulfonated azo dye Reactive Orange 16 (RO16) efficiently. Superoxide dismutase and catalase activity were tested to study the response of Lysinibacillus sp. RGS to the oxidative stress generated by RO16. The results demonstrated that oxidative stress enzymes not only protect the cell from oxidative stress but also has a probable role in decolorization along with an involvement of oxidoreductive enzymes. Formation of three different metabolites after degradation of RO16 has been confirmed by GC-MS analysis. FTIR analysis verified the degradation of functional groups of RO16, and HPTLC confirmed the removal of auxochrome group from the RO16 after degradation. Toxicity studies confirmed the genotoxic, cytotoxic, and phytotoxic nature of RO16 and the formation of less toxic products after the treatment of Lysinibacillus sp. RGS. Therefore, Lysinibacillus sp. RGS has a better perspective of bioremediation for textile wastewater treatment.     

Factors affecting degradation of dimethyl sulfoxide (DMSO) by fluidized-bed Fenton process

In this study, the target compound is dimethyl sulfoxide (DMSO), which is used as a photoresist stripping solvent in the semiconductor and thin-film transistor liquid crystal display (TFT-LCD) manufacturing processes. The effects of the operating parameters (pH, Fe²⁺ and H₂O₂ concentrations) on the degradation of DMSO in the fluidized-bed Fenton process were examined. This study used the Box-Behnken design (BBD) to investigate the optimum conditions of DMSO degradation. The highest DMSO removal was 98 % for pH 3, when the H₂O₂ to Fe²⁺ molar ratio was 12. At pH 2 and 4, the highest DMSO removal was 82 %, when the H₂O₂ to Fe²⁺ molar ratio was 6.5. The correlation of DMSO removal showed that the effect of the parameters on DMSO removal followed the order Fe²⁺?>?H₂O₂?>?pH. From the BBD prediction, the optimum conditions were pH 3, 5 mM of Fe²⁺, and 60 mM of H₂O₂. The difference between the experimental value (98 %) and the predicted value (96 %) was not significant. The removal efficiencies of DMSO, chemical oxygen demand (COD), total organic carbon (TOC), and iron in the fluidized-bed Fenton process were higher than those in the traditional Fenton process.     

Combined effects of DOM and biosurfactant enhanced biodegradation of polycylic armotic hydrocarbons (PAHs) in soil–water systems

This study systematically investigated the interactive effects of dissolved organic matter (DOM) and biosurfactant (rhamnolipid) on the biodegradation of phenanthrene (PHE) and pyrene (PYR) in soil–water systems. The degradations of two polycyclic aromatic hydrocarbons (PAHs) were fitted well with first order kinetic model and the degradation rates were in proportion to the concentration of biosurfactant. In addition, the degradation enhancement of PHE was higher than that of PYR. The addition of soil DOM itself at an environmental level would inhibit the biodegradation of PAHs. However, in the system with co-existence of DOM and biosurfactant, the degradation of PAHs was higher than that in only biosurfactant addition system, which may be attributed to the formation of DOM–biosurfactant complex micelles. Furthermore, under the combined conditions, the degradation of PAH increased with the biosurfactant concentration, and the soil DOM added system showed slightly higher degradation than the compost DOM added system, indicating that the chemical structure and composition of DOM would also affect the bioavailability of PAHs. The study result may broaden knowledge of biosurfactant enhanced bioremediation of PAHs contaminated soil and groundwater.     

Removal of Rhodamine B under visible irradiation in the presence of Fe⁰, H₂O₂, citrate and aeration at circumneutral pH

A new Vis-Fe⁰-H₂O₂-citrate-O₂ system comprising zero-valent iron, hydrogen peroxide, citrate anion and aeration at circumneutral pH under visible irradiation was studied. 21 μmol L⁻¹ of Rhodamine B (RhB) was chosen as the substrate to be tested. Experiments were conducted under conditions of 2.9 mmol L⁻¹ of H₂O₂, 12.6 g of Fe⁰ and 1.0 mmol L⁻¹ of citrate at pH 7.5. Results showed that, in 1 h reaction, 54% of RhB was removed with corresponding 26% of COD reduced. Meanwhile, the amount of released dissolved irons from Fe⁰ surface was found to be at a very low level as <5.4 μmol L⁻¹. Extinguishing tests with isopropanol suggested that RhB oxidation by hydroxyl radicals was the main process taken place in Vis-Fe⁰-H₂O₂-citrate-O₂ system, which accounted for 75% of substrate removal in 3 h reaction. Control and factor influencing experiments showed that the prohibitive extents of individual factor importance on RhB removal followed a decreasing order of Fe⁰ > H₂O₂ > citrate > Vis > O₂. This study showed an excellent system that could remove refractory organic compounds from water in laboratory researches, and also provided a good idea to reduce secondary contamination by dissolved irons in future investigations.     

Enhanced bioremediation of soil from Tianjin,China, contaminated with polybrominated diethyl ethers

This work aimed to evaluate the effectiveness of nutrients, H₂O₂, and tourmaline on the bioremediation of fields where the soil was contaminated with polybrominated diethyl ethers (PBDEs). The results showed that 39.2, 38.3, and 48.1 % of total PBDE removal was observed in microcosms with the addition of nutrients, such as NaNO₃, NH₄Cl, and NH₄NO₃, respectively, compared to only 15.2 and 5.8 % of PBDE removal from soil with added Aspergillus niger and control soil, respectively, after 50 days of incubation. In addition, 50.8 and 56.5 % of total PBDE removal were observed in microcosms with 0.5 and 1 μL H₂O₂. The addition of tourmaline increased total PBDE removal to 32.4 %. Significant increases in soil enzymatic activity with PBDE degraders and bacterial communities were observed using polymerase chain reaction (PCR)—denaturing gradient gel electrophoresis (DGGE). These observations suggested that the combination of inorganic nutrients with chemical, mineral, and biological treatment could improve the PBDE removal efficiency. However, the combination of H₂O₂ and biological treatment processes is the most efficient technology. This combination of technologies would not cause adverse effects on the subsequent bioremediation process. Therefore, this work offers a potential alternative for the remediation of soil contaminated with PBDE pollutants.     

Biodegradation assessment of PLA and its nanocomposites

Poly(lactic acid) nanocomposites containing Cloisite 15A, Cloisite 30B, and Dellite 43B were prepared by melt-mixing in a batch mixer and were exposed to UV radiation, temperature, and microorganism in solution and in a compost. Exposed samples, collected along the time, were characterized by several techniques. While the addition of organoclays had a positive effect on thermal stability, the degradation rate of nanocomposites increased when exposed to UV radiation and microorganism. Moreover, the degradation rate depends on the organoclay type. Even though the degradation rate is higher for nanocomposites, Fourier transform infrared spectrometry and gel permeation chromatography results demonstrated that the degradation mechanism is the same.     

Environmental photochemistry of fluoroquinolones in soil and in aqueous soil suspensions under solar light

The photodegradation fate of widely used fluoroquinolone (FQ) drugs has been studied both at the water–soil interface and in soil at actual concentrations (500 ng g^?1) under natural solar light. Both human and veterinary drugs have been examined, namely ciprofloxacin, danofloxacin, enrofloxacin, levofloxacin, marbofloxacin and moxifloxacin. After spiking and irradiation, samples were submitted to microwave-assisted extraction and analyzed by high-performance liquid chromatography coupled to fluorescence detection (HPLC–FD). FQs degradation was faster in aqueous soil suspension than in neat soil (but lower than in “clean” water). A number of byproducts were identified by HPLC electrospray ionization tandem mass spectrometry after a post-extraction cleanup based on a molecularly imprinted polymer phase, for a more accurate detection. The distribution in the suspension was intermediate between those observed in soils and in aqueous solutions.     

Application of the triolein-embedded cellulose acetate membrane passive sampler for monitoring of polycyclic aromatic hydrocarbons in water

Triolein-embedded cellulose acetate membrane (TECAM) can be used as a passive sampler to measure hydrophobic organic contaminants in water. Uptake constant rates (k _u ) for polycyclic aromatic hydrocarbons (PAHs) by TECAM sampling were measured under different hydrodynamic conditions. The measured k _u values were modeled to enable the quantification of time weighed average (TWA) concentrations of PAHs in the field. An empirical relationship that enables the calculation of in situ k _u values of chemicals using performance reference compounds (PRCs) was derived and its application was demonstrated in a field study. The results showed that freely dissolved concentrations of hydrophobic organic compounds (HOCs) can be accurately measured in the field using TECAM method based on empirical uptake models calibrated with PRCs.     

Preparation,characterization, and photocatalytic activity evaluation of Fe–N-codoped TiO2/fly ash cenospheres floating photocatalyst

Nitrogen-doped titanium dioxide (TiO₂) and Fe–N-codoped TiO₂ layers on fly ash cenospheres (FAC) as floating photocatalyst were successfully prepared through sol–gel method. Photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), ultraviolet (UV)–Vis diffuse reflectance spectroscopy (DRS), and nitrogen adsorption analyses for Brunauer–Emmett–Teller (BET) specific surface area. Photocatalytic efficiency of the prepared catalyst was evaluated through using the decomposition of Rhodamine B (RhB) as a model compound under visible light irradiation. Photocatalytic activity and kinetics of catalyst under visible light were detected in details from different Fe/Ti mole ratios by detecting photodegradation of RhB. Experimental results show that when the calcination temperature was 550 °C, the dosage of FAC was 3.0 g, and the mole ratio of Fe/Ti was 0.71 %; the synthesized Fe–N-TiO₂/FAC photocatalyst presented as anatase phase and that N and Fe ions were doped into TiO₂ lattice. The material’s specific surface area was 34.027 m²/g, and UV–Vis diffuse reflectance spectroscopy shows that the edge of the photon absorption has been red shifted up to 400–500 nm. Fe–N-codoped titanium dioxide on FAC had excellent photocatalytic activity during the process of photodegradation of RhB under visible light irradiation.

     

Distribution,possible sources,and health risk assessment of SVOC pollution in small streams in Pearl River Delta,China

The pollution levels of typical semivolatile organic compounds (SVOCs) consisting of 15 polycyclic aromatic hydrocarbons (PAHs), 20 organic chlorinated pesticides (OCPs), and 15 phthalate esters (PAEs) were investigated in small rivers running through the flourishing cities in Pearl River Delta region, China. The concentrations of ∑15PAHs were 2.0–48 ng/L and 29–1.2?×?10³ ng/g in the water and sediment samples, respectively. The ∑20OCPs were 6.6–57 ng/L and 9.3–6.0?×?10² ng/g in the water and sediment samples, respectively. The concentrations of ∑15PAEs were much higher both in the water and sediments. The partition process of the detected SVOCs between the water and sediment did not reach the equilibrium state at most of the sites when sampling. The combustion of petroleum products and coal was the major source of the detected PAHs. The OCPs were mainly historical residue, whereas the new inputs of dichlorodiphenyltrichloroethane (DDT), chlordane, and endosulfan were possible at several sites. The industrial and domestic sewage were the major source for the PAEs; storm water runoff accelerated the input of PAEs. No chronic risk of the SVOCs was identified by a health risk assessment through daily water consumption, except for the ∑20OCPs that might cause cancer at several sites. Nevertheless, the integrated health risk of the SVOCs should not be neglected and need intensive investigations.     

Contamination and distribution of parent,nitrated, and oxygenated polycyclic aromatic hydrocarbons in smoked meat

Smoked meat is widely consumed in many areas, particularly in rural southwest China. High concentrations of polycyclic aromatic hydrocarbons (PAHs) in smoked meat could lead to adverse dietary exposure and health risks. In this study, 27 parent PAHs (pPAHs), 12 nitrated PAHs (nPAHs), and 4 oxygenated PAHs (oPAHs) were measured in coal- and wood-smoked meats. The median concentrations of pPAHs, nPAHs, and oPAHs were as high as 1.66?×?10³, 4.29, and 20.5 ng/g in the coal-smoked meat and 2.54?×?10³, 7.32, and 9.26 ng/g in the wood-smoked meat, respectively. Based on the relative potency factors of individual PAHs, the calculated toxic equivalent (TEQ) values of all pPAHs were 22.1 and 75.1 ng TEQ/g for the wood- and coal-smoked meats, respectively. The highest concentrations of PAHs can be found in the surface layer of skin and decrease exponentially with depth. Surface PAH concentrations correlated with concentrations of PAHs in household air and with the concentration in emission exhaust. Migration of PAHs from surface to interior portions of meat is faster in lean than in fat or skin, and oPAHs and pPAHs can penetrate deeper than pPAHs. The penetration ability of PAHs is negatively correlated with the molecular weight.     

Spatial distribution,potential risk assessment,and source apportionment of polycyclic aromatic hydrocarbons (PAHs) in sediments of Lake Chaohu,China

Twenty-nine sediment samples were collected from Lake Chaohu, a shallow eutrophic lake in Eastern China, and were analyzed for 15 priority polycyclic aromatic hydrocarbons (PAHs) to determine the spatial distribution and exposure risks of PAHs. Three receptor models, the principal component analysis-multiple linear regression (PCA-MLR) model, the positive matrix factorization (PMF) model, and the Unmix model, were used in combination with the PAHs diagnostic ratios to investigate the potential source apportionment of PAHs. A clear gradient in the spatial distribution and the potential toxicity of PAHs was observed from west to east in the sediments of Lake Chaohu. ∑₁₅PAH concentrations and the TEQ were in the range of 80.82-30 365.01 ng g^?1 d.w. and 40.77-614.03, respectively. The highest values of the aforementioned variables were attributed to urban–industrial pollution sources in the west lake region, and the levels decreased away from the river inlets. The three different models yielded excellent correlation coefficients between the predicted and measured levels of the 15 PAH compounds. Similarly, source apportionment results were derived from the three receptor models and the PAH diagnostic ratios, suggesting that the highest contribution to the PAHs was from coal combustion and wood combustion, followed by vehicular emissions. The PMF model yielded the following contributions to the PAHs from gasoline combustion, diesel combustion, unburned petroleum emissions, and wood combustion: 34.49, 24.61, 16.11, 13.01, and 11.78 %, respectively. The PMF model produced more detailed source apportionment results for the PAHs than the PCA-MLR and Unmix models.